Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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OVERLAMINATE FILMS
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application claims the benefit of U.S.
Provisional Application
No. 61/921,571 filed on December 30, 2013, which is incorporated herein by
reference in its
entirety.
BACKGROUND OF THE INVENTION
[0002] Overlaminates may be placed over various materials, such as
printing
materials, to protect the underlying material from damage. In some instances,
overlaminates
may be placed over signs and banners having text or graphics, such as for
advertising and
decorations. The present invention includes overlaminates for these purposes
and any other
suitable purposes.
SUMMARY OF THE INVENTION
[0003] In one embodiment, the invention includes an overlaminate
film. The
overlaminate film may include a skin layer comprising an abrasion resistant
material, a core
layer comprising a blend of one or more semicrystalline polymer and ethylene
vinyl acetate,
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and an adhesive layer. In addition, the core layer may be positioned between
the skin layer and
the adhesive layer.
[0004] In another embodiment, the invention includes an
overlaminate film.
The overlaminate film may include a skin layer comprising an abrasion
resistant material and an
adhesive layer. In addition, the overlaminate film may include a core layer
that includes a blend
of (i) one or more of an amorphous olefin copolymer having either a glass
transition
temperature (Tg) in the range of about 20 C to about 70 C (including each
intermittent value
therein), or a semicrystalline olefin copolymers having a melting point in the
range of about
20 C to about 70 C including each intermittent value therein), and (ii) a
polyolefin. The core
layer may be positioned between the skin layer and the adhesive layer.
[0005] The following description illustrates one or more
embodiments of the
invention and serves to explain the principles and exemplary embodiment of the
invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Fig. 1 depicts an embodiment of an overlaminate film of the
present
invention;
[0007] Fig. 2 depicts an additional embodiment of an overlaminate
film of the
present invention;
[0008] Fig. 3 depicts an additional embodiment of an overlaminate
film of the
present invention;
[0009] Fig. 4 depicts an embodiment of an overlaminate film of the
present
invention as applied to a print layer;
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[0010] Fig. 5 depicts overlapping segments of two pieces of
overlaminated print
layers a on substrate;
[0011] Fig. 6 is a DMA curve for samples evaluated;
[0012] Fig. 7 is a graph comparing optical properties of samples
tested;
[0013] Fig. 8 is a graph of modulus data for samples tested;
[0014] Fig. 9 is an illustrative image of a film exhibiting
tunneling effects; and
[0015] Fig. 10 is a flow chart illustrating films orientation at
overlapping area as
referenced herein.
DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS
[0016] Reference will now be made in detail to exemplary
embodiments of the
present invention, one or more examples of which are illustrated in the
accompanying
drawings. Each example is provided by way of explanation of the invention and
not by
limitation of the invention. It will be apparent to those skilled in the art
that modifications and
variations can be made in the present invention without departing from the
scope or spirit
thereof. For instance, features illustrated or described as part of one
embodiment may be used
on another embodiment to yield a still further embodiment. Thus, it is
intended that the
present invention covers such modifications and variations as come within the
scope of the
appended claims and their equivalents. In addition, the use of reference
characters with the
same two ending digits as other reference characters to indicate structure in
the present
specification and drawings, without a specific discussion of such structure,
is intended to
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represent the same or analogous structure in different embodiments. Unless
otherwise
indicated herein, all percentages used for a component refer to the percentage
by weight.
[0017]
In some embodiments, the present invention includes a film
overlaminate. In some embodiments, such overlaminates may include at least one
skin layer
that is an abrasion resistance layer, at lease one core layer, and at least
one skin layer
referenced as an adhesive layer. By way of example to an illustrative
embodiment, Fig. 1 shows
an overlaminate 100 having a skin layer 102, a core layer 104, and an adhesive
layer 106. In
some embodiments, a film may have multiple skin layers and/or multiple core
layers. In still
other embodiments, films of the present invention may include additional
layers.
[0018]
As indicated above, one or more skin layers of the overlaminate may
include an abrasion resistance layer. Such abrasion resistant layers may be
comprised of any
suitable abrasion resistant material.
For example, in some embodiments, an abrasion
resistance layer may include Surlyn products available from DuPont, including
Surlyn 1803.
Other suitable abrasion resistant materials that form or be included in the
abrasion resistance
layer include ethylene acrylic polymers and copolymers. In other embodiments,
other suitable
materials may be used that provide suitable abrasion resistance for a
particular application of a
film.
[0019]
In some embodiments, skin layers, including abrasion resistant layers,
may also include one or more matting agents (also called gloss reducers), such
as DU_ 3636
DP20 from A. Schulman Inc and/or Ampacet 400700D from Ampacet Corp. in amount
ranging
from about 1% to about 50% by weight of the total skin layer. Such matting
agents may provide
a matte finish to the film.
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[0020] In some embodiments, skin layers, including abrasion
resistant layers,
may also include one or more stabilizers, such as the ultraviolet ("UV") light
stabilizer Ampacet
UV 10561, which is available from Ampacet Corporation. By way of further
example, a skin
layer may also include free radical scavengers. Free radical scavengers, such
as hindered amine
light stabilizer (HALS), may be present, alone or in addition to UV light
stabilizers, in an amount
of about 0.05 to about two weight percent per layer, and the UV light
stabilizers, such as
benzophenone, can be present in amounts ranging from 0.1 to about 5 weight
percent per
layer. Such ultraviolet light stabilizers and/or free radical scavengers may
be included in some
or all of the skin layers of a particular embodiment.
[0021] In addition, one or more skin layers of the present
invention may also
include and one or more process aids, such as Ampacet 10919 available from
Ampacet
Corporation. Furthermore, in some embodiments, one or more skin layers may
include a flame
retardant compound. By way of example, such a flame retardant may include FRC-
2005 (which
is a flame retardant and ultraviolet stabilizer that is available from Polyfil
Corporation).
[0022] Similarly, one or more skin layers of the present invention
may also or
alternatively include heat stabilizers. Heat stabilizers may include Ferro
1237, Ferro 1720, and
Synpron 1163, all available from Ferro Corporation Polymer Additives Division,
and Mark V
1923, available from Witco Corp. By way of example, heat stabilizers may be
present in an
amount from about 0.2 to about 0.15 percent by total weight of a print layer,
including each
intermittent value therein. In embodiments having multiple skin layers, such
heat stabilizers
may be included in some or all of the skin layers.
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[0023] In some embodiments of the present invention, an
overlaminate may
include at least two skin layers. In addition, some embodiments may include at
least two skin
layers that are abrasion resistant layers. Other embodiments may have more
than two skin
layers, wherein some or all of such additional skin layers may optionally be
abrasion resistant
layers. In addition, as set forth herein, some embodiments may also include a
top coating.
[0024] Laminates of the present invention may also include at least
one core
layer. As shown in Fig. 1 and described above, a core layer may be positioned
in the laminate
between the abrasion resistance layer and the adhesive layer. In one
embodiment, at least one
layer of a core layer comprises a blend of (i) one or more semicrystalline
polymers, and (ii)
ethylene vinyl acetate. Suitable semicrystalline polymers may include, by way
of example,
semicrystalline polymers such as polyethylene. In one embodiment of the
present invention,
the core layer may include a blend of medium density polyethylene and ethylene
vinyl acetate.
In another embodiment, the core layer may include a blend of high density
polyethylene and
ethylene vinyl acetate. In still other embodiments, the core layer may include
a blend of
medium density polyethylene, high density polyethylene, and ethylene vinyl
acetate. The
desired stiffness of a film may be controlled, at least in part, by the type
and amount of
polymer included. For example, high density polyethylene results in increased
stiffness of the
film at room temperature as compared with medium density polyethylene. In
certain
embodiments of the present invention, core layers may comprise from about 5%
to about 95%
by weight semicrystalline polymers and about 5% to about 95% by weight
ethylene vinyl
acetate. In some embodiments, a core layer may comprise at least about 13% by
weight
ethylene vinyl acetate.
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[0025] In still other embodiments, other suitable compositions may
be used for
one or more layers of a core layer. For example, in one particular embodiment,
a core layer
may be formed from or comprised of a blend of (i) an amorphous olefin
copolymer having a
glass transition temperature (Tg) in the range of about 20 C to about 70 C
(including each
intermittent value therein), and/or a semicrystalline olefin copolymer having
a melting point in
the range of about 20 C to about 70 C (including each intermittent value
therein), and (ii) a
polyolefin, such as, for example, polypropylene. Any suitable amorphous olefin
copolymer may
be used. For example, in some embodiments, cyclic olefin copolymers (COC),
such as_Topas
9903 D-10 with a Tg of 33 C, which is available from TOPAS Advanced Polymers,
may be used as
a suitable amorphous olefin copolymer. For example, in some embodiments,
ethylene
polypropylene copolymer, such as Versify 2300 melting temperature of 66 C,
which is available
from Dow Chemical, may be used as suitable semicrystalline olefin copolymer.
Such layers¨
comprised of a blend of (i) an amorphous olefin copolymer having either a
glass transition
temperature (Tg) in the range of about 20 C to about 70 C (including each
intermittent value
therein), and/or a semicrystalline olefin copolymer having a melting point in
the range of about
20 C to about 70 C including each intermittent value therein), and (ii) a
polyolefin¨may
comprise the entire core layer, one layer of a multilayer core layer, or
multiple or all layers of a
multilayer core layer. By way of example, in certain embodiments of the
present invention,
core layers may comprise about 5 to about 100 percent by weight of an
amorphous olefin
copolymer and about 0 to about 95 percent by weight polyolefin. In some
embodiments, core
layers may comprise at least about 20 percent by weight of an amorphous olefin
copolymer.
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[0026] Core layers of the present invention may also include other
components.
For example, some or all layers of a core layer may include one or more
ultraviolet light
stabilizers, one or more free radical scavengers, one or more process aids,
one or more heat
stabilizers, and/or one or more flame retardants. Such components may be
included a core
layer as described above with respect to the skin layers.
[0027] In some embodiments of the present invention, a core layer
may have
multiple layers. For example, in some embodiments, a multilayer core layer may
have three
layers, such as a first core layer, a second core layer, and a third core
layer. By way of example,
a second core layer of a multilayer core layer may be located between a skin
layer, such as an
abrasion resistance layer, and a first core layer, and a third core layer of a
multilayer core layer
may be located between the first core layer and the adhesive layer. The second
core layer and
the third core layer may each have the same composition of the first core
layer in some
embodiments, and in other embodiments the second core layer and/or the third
core layer may
have distinct compositions from the first core layer. In some embodiments, the
second core
layer and/or the third core layer may be less thick than the first core layer
and/or may (each or
collectively) constitute a lesser weight percentage of a film than the core
layer.
[0028] For example, in one embodiment, the middle layer of a three-
layer core
layer may be a blend of medium density polyethylene with ethylene vinyl
acetate, and the
outer layers of the three-layer core layer may be a blend of blend of high
density polyethylene
and ethylene vinyl acetate. In still other embodiments, a multi-layer core
layer may have
multiple adjacent layers having the same composition as a central layer of the
core layer.
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[0029] Using film compositions as described herein, certain
overlaminate
embodiments of the present invention may be suitably rigid at room temperature
for handling
purposes. In addition, certain overlaminate embodiments of the present
invention may provide
sufficient structural behavior such that at increased temperatures tunneling
does not
substantially occur or does not occur, as described in more detail herein.
[0030] As indicated above, overlaminates of the present invention
may also
include an adhesive layer. Such adhesive layers may provide a surface to which
any suitable
adhesive may be added and may comprise any suitable material. In some
embodiments, an
adhesive layer may include a polymer resin, such as a low density olefin
homopolymer resin.
For example, Petrothene NA 324-009, available from LyondellBasell, and/or a
low density or
linear low density polyethylene, such as Dowlex 2036G available from The Dow
Chemical
Company, may be used to form an adhesive layer in some embodiments of the
present
invention. The adhesive layer may also include ethylene vinyl acetate. In some
embodiments,
the adhesive layer may also include stabilizers, such as the ultraviolet light
stabilizer Ampacet
UV 10561 (available from Amapcet Corporation) and/or FR-2005 (which is a flame
retardant
and ultraviolet stabilizer and available from Polyfil Corporation). In
addition, an adhesive layer
may include one or more process aids, such as Ampacet 10919. The adhesive
layer may also
include heat stabilizers, ultraviolet light stabilizers, and free radical
scavengers as discussed
above. In some embodiments, adhesive, such as a pressure sensitive adhesive,
may be applied
to an adhesive layer and a release liner may optionally be located adjacent to
an adhesive layer,
such that the release layer is suitable for removal prior to and at the time
of application of the
overlaminate.
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[0031]
Overlaminates of the present invention may be used with any suitable
underlying material, such as to protect an underlying print film. A pressure
sensitive adhesive
may be used between the overlaminate and the underlying print film. The
pressure sensitive
adhesive may adhere to the adhesive layer of the overlaminate. Prior to
application of the
overlaminate to a print film, the overlaminate may have a releasable liner
adjacent to the
adhesive.
[0032]
In some embodiments, overlaminates of the present invention may be
substantially free of polyvinyl chloride (PVC). In other embodiments,
overlaminates of the
present invention may not include any PVC. In some embodiments, such
substantially PVC-free
or PVC-free overlaminates may be used as an overlaminate on an underlying
material that does
is either free or substantially free of PVC.
In some embodiments, by way of example,
overlaminates of the present invention may be used on an underlying material
such as True
Impact TMP7000 materials, available from Avery Dennison Corporation.
[0033]
In one embodiment, as shown in Fig. 2, an overlaminate 200 may include
a first skin layer 202 and a second skin layer 202, wherein one or both may be
an abrasion
resistant layer, a core layer 204, and an adhesive layer 206. In an
alternative embodiment, as
shown in Fig. 3, an overlaminate 300 may include a first skin layer 302' and a
second skin layer
302, wherein one or both may be an abrasion resistant layer, a three-layer
core layer including
a first core layer 304, a second core layer 304, and third core layer 304, and
an adhesive layer
306. As explained above, some embodiments may also include an adhesive (not
shown) in
contact with adhesive layer 306 and, optionally, a release liner (not shown)
in contact with the
adhesive.
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[0034]
In still other embodiments, an overlaminate of the present invention may
include a tie layer positioned between a core layer and a skin layer, such as
an abrasion
resistance layer. A tie layer may include ethylene vinyl acetate, and, in some
embodiments, a
tie layer may comprise all or substantially all ethylene vinyl acetate. In
some embodiments, a
tie layer may also include some or all layers of a core layer may include one
or more ultraviolet
light stabilizers, one or more free radical scavengers, one or more process
aids, one or more
heat stabilizers, and/or one or more flame retardants. Such components are
described above
with respects to the skin layers and may be included in tie layers in the same
manner.
[0035]
In addition, some embodiments of laminates of the present invention
may be entirely free of polyvinyl chloride ("PVC"). In other embodiments,
laminates of the
present invention may be substantially free of polyvinyl chloride. In such
embodiments entirely
free or substantially free of polyvinyl chloride, laminates of the present
invention may offer
satisfactorily-similar properties to known polyvinyl chloride laminates.
[0036]
Overlaminates of the present invention may be suitable for indoor and/or
outdoor use. Such overlaminates may provide suitable and desirable durability,
scratch
resistance, gloss, conformability, tensile elongation and tensile strength for
such applications.
In addition, overlaminates of the present invention may have a glossy finish
or a matte finish.
[0037]
Overlaminates of the present invention may be applied over a print layer,
which may include text and graphics such as for advertising or decoration. For
example, as
shown in Fig. 4, overlaminate 400 may be applied over a print layer 450. A
pressure sensitive
adhesive may be disposed between overlaminate 400 and print layer 450.
In other
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embodiments, a print layer may be multiple layers and may be of any suitable
composition
known in the art.
[0038] In some embodiments, such as due to the size of large
banners or
displays, an overlaminated print layer may be provided in segments that
overlap to form a
single display, such as shown in Fig. 5. For example, as shown in Fig. 5,
overlaminate layer 400
(which may, in some embodiments, be a multilayer film as described herein) is
affixed to print
layer 452 using adhesive 412. As shown, one segment of the overlaminated print
layer overlaps
with another segment of an overlaminated print layer, and each segment is
affixed to substrate
453 using adhesive 452, which may be the same or different as adhesive 412. As
such,
overlaminate 400 (which may be a multilayer film as described herein) is laid
over each
segment and affixed to the print layer using adhesive 412. Some such
overlapping
overlaminates are known to result in "tunneling" when exposed to high
temperatures, such as
high outdoor temperatures, especially in the summer season. Tunneling
indicates a separation
or buckling of the overlaminate from the underlying substrate (such as print
layer 450), such
that a hump or unevenness is formed. An example of tunneling is shown in Fig.
9. In addition,
tunneling may also include a separation or lifting of an overlaminate and any
underlying
substrate from a material to which they are applied. Tunneling may often
result from
temperature variations and fluctuations. In some embodiments as indicated in
the illustrative
examples below, overlaminates of the present invention may not tunnel when
exposed to
temperature variations, such as when used in an outdoor setting. Using certain
embodiments
of the present invention, tunneling may be diminished or eliminated. In
addition, films of the
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present invention may also provide a sufficiently stiff film at room
temperature to render
handling by a user satisfactory.
[0039]
The following examples further illustrate embodiments and features of
the invention. The following components may be referenced in these examples:
Component Description
Surlyn 1803 lonomer resins of ethylene copolymers
containing acid groups partially neutralized
using metal salts. Family of ionomers are
partially neutralized by metals such as zinc,
sodium, and others. Other ionomers that can
be used include packaging grade ionomers
such as Surlyn 1705, 1601, 1901, 1857 as well
as golf ball grade 9120.
Ampacet Process Aid
Process aid masterbatch in polyethylene
supplied by Ampacet Corporation
Ampacet UV 10561
UV absorber in LDPE, supplied by Ampacet
Corporation
Petrothene NA324-009
Low density homopolymer with density of
0.931 supplied by Equistar Corporation
FRC-2005
Flame retardant/UV absorber in polyethylene
supplied by Polyfil Corporation
Dow DMTA -8904 NT 7
High density polyethylene with a density of
0.952 from Dow Chemical
Dowlex 2036G
Linear low density polyethylene with density
of 0.935 supplied by Dow Chemical
Huntsman LDPE 1017
Low density polyethylene with density of 9.2
available from Huntsman Corporation.
Topas 9903 D-10
Cyclo olefin copolymer with a Tg of 33 C
supplied by Topas Advanced Polymers
Topas 9506F-04
Cyclo olefin copolymer with a Tg of 65 C
supplied by Topas Advanced Polymers
Example 1
[0040]
A multilayer overlaminate film with an overall thickness of 2.5 mils was
produced using a conventional 4-layer cast film co-extrusion process. Each of
the four
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extruders (A, B, C, and D) supplied a melt formulation to a feedblock where
the melts were
combined to form a single molten stream consisting of four different layers.
Extruder A was fed
with material that formed a skin layer, also referenced as an abrasion
resistant layer, Extruder C
was fed with a molten layer that formed the core layer, and Extruder D was fed
with the
adhesive layer. As reflected in Table I, Extruder B was fed with either the
same material as
Extruder C that also formed the core layer or, alternatively, material that
formed a tie layer. In
the resulting films without a tie layer, the skin layer formed about 10% of
the overall film
thickness, the core layer (from Extruders B and C) formed a total of about 80%
of the overall
film thickness, and the adhesive layer formed about 10% of the overall film
thickness. In the
resulting films with a tie layer, the skin layer formed about 10% of the
overall film thickness, the
tie layer formed about 10% of the overall film thickness, the core layer
formed about 70% of
the overall film thickness, and the adhesive layer formed about 10% of the
overall film
thickness. For each sample, the molten stream was cast onto a cast roll with a
chrome finish
and an airknife at 60 Hz was used to pin the quenched film to the chrome roll.
Table I shows
the formulations used in the different extruders, wherein the percentages are
by weight.
Table l
immilkintave riogoomiiiNTteitayernmami
aimiiiiiiiiiloretaverimimmimAdhesivetayeram
1 93 % Surlyn 1803 None 73 % Petrothene 62 % Petrothene
% Ampacet UV NA324-009 NA324-009
2 % Ampacet 25 % Ethylene vinyl 35 % Ethylene
vinyl
Process Aid acetate acetate
1 % Ampacet UV 1 % Ampacet UV
10561 10561
1 % Ampacet 2 % Ampacet
Process aid Process aid 10919
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2 93 % Surlyn 1803 None 98 % Petrothene 62 % Petrothene
% Ampacet UV NA324-009 NA324-009
2 % Ampacet 1 % Ampacet UV 35 % Ethylene
vinyl
Process Aid 10561 acetate
1 % Ampacet 1 % Ampacet UV
Process aid 10561
2 % Ampacet
Process aid 10919
3 93 % Surlyn 1803 93 % Ethylene vinyl 98 % Petrothene 62 % Petrothene
5 % Ampacet UV acetate NA324-009 NA324-009
2 % Ampacet 5 % Ampacet UV 1 % Ampacet UV 35 % Ethylene
vinyl
Process Aid 2 % Ampacet 10561 acetate
Process Aid 1 % Ampacet 1 % Ampacet UV
Process aid 10561
2 % Ampacet
Process aid 10919
4 93 % Surlyn 1803 93 % Ethylene vinyl 98 % Dowlex 2036G 62 % Dowlex
2036G
5 % Ampacet UV acetate 1 % Ampacet UV 35 % Ethylene
vinyl
2 % Ampacet 5 % Ampacet UV 10561 acetate
Process Aid 2 % Ampacet 1 % Ampacet 1 % Ampacet UV
Process Aid Process aid 2 % Ampacet
Process aid
5 93 % Surlyn 1803 None 98 % Dowlex 2036G 62 % Dowlex 2036G
5 % Ampacet UV 1 % Ampacet UV 35 % Ethylene
vinyl
2 % Ampacet 1 % Ampacet acetate
Process Aid process aid 1 % Ampacet UV
2 % Ampacet
Process aid
6 93 % Surlyn 1803 None 85 % Petrothene 77 % Petrothene
5 % Ampacet UV NA324-009 NA324-009
2 % Ampacet 13 % Ethylene vinyl 20 % Ethylene
vinyl
Process Aid acetate acetate
1 % Ampacet UV 1 % Ampacet UV
10561 10561
1 % Ampacet 2 % Ampacet
Process aid Process aid 10919
[0041] The laminate films from Table l were coated on the adhesive
layer with
adhesive S8072, which is an acrylic-based adhesive sold by Avery Dennison
Corporation and
which also is used in the vinyl overlaminate sold by Avery Dennison
Corporation under the
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trade name DOL 2060. The adhesive-coated films were laminated to a non-PVC
print film sold
by Avery Dennison Corporation as TrueImpact (TMP) 7000 series, which has S-
8072 adhesive on
its back surface. One segment of overlaminated print film was applied on a
surface coated
automotive panel using a soft squeegee to ensure that an intimate contact was
made between
the graphic laminate and the substrate, then another segment of overlaminated
print film was
applied on the same panel such that an overlap was formed at the joint area as
illustrated in
Fig. 5 such that an overlap seam was created. In addition, the seams were made
such that they
were either parallel to the machine direction of the film or parallel to the
cross-direction of the
film.
[0042] Each laminated panel sample was left at room temperature for
at least
twenty-four hours before being tested for tunneling to ensure the strong
adhesion build-up
between film and panel. Tunneling was known to result after temperature
cycling as described
above.
[0043] Tunneling testing was done by placing the samples in an oven
that was
preheated to 70 C. The samples were left in the oven for at least thirty
minutes and were
examined for any sign of tunneling. After the initial assessment, the samples
were placed in the
oven for at least twenty-four hours before a second evaluation. Films were
examined with a
seam orientation in the machine direction and with a seam orientation in the
cross direction, as
illustrated in Fig. 10. The extent of tunneling was ranked based on the level
of buckling of the
film. As indicated in Table II, a ranking of 1 indicates that the film did not
lift or buckle when
exposed to the temperature swings and a ranking of 5 indicates the worst
observations of
tunneling with pronounced buckling. The results are shown below in Table II.
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Table II
Sari...........................................................................
......................
mumwmwmorientatioluimiocommentsmiNigii*iiRankingii:
Sample 1 MD No tunneling 1
Sample 1 CD No tunneling 1
Sample 2 MD No tunneling 1
Sample 2 CD Slight tunneling 3
Sample 3 MD Shows tunneling 5
Sample 3 CD Shows tunneling 5
Sample 4 MD Shows tunneling 5
Sample 4 CD Shows tunneling 5
Sample 5 MD No tunneling 1
Sample 5 CD Shows tunneling 5
Sample 6 MD Slight tunneling 3
Sample 6 CD Slight tunneling 3
[0044] As shown by the results in Table II, tunneling was not
observed at the
seam of laminate samples (in either the machine direction or cross-direction
samples) having
ethylene vinyl acetate in the core layer.
Example II
[0045] In this example, Sample 7 had the same formulation and was
prepared in
the same manner as Sample 1. Sample 7 was compared with commercially-available
products
for tunneling properties. The commercially-available products are shown in the
table below.
The Avery Dennison samples, namely DOL 2060, TOL 7060, and PE85, are available
from Avery
Dennison Corporation. The 3M 8548 Envision Gloss sample is available from 3M.
Except for
the 3M 8548 Envision gloss sample (which includes an adhesive), each sample
was coated with
an adhesive before being laminated over TrueImpact (TMP) 7000 (also available
from Avery
Dennison), which also was coated with the same adhesive. Each laminate was
then applied
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onto a coated metal panel as described in Example I. The results are provided
in Table III using
the same ranking scale provided above.
Table III
iiiwooSgttftteWS.atkltg.ettegttiOtkinMMMTLititfetiifgt.tttilittritWMNWiNim
...Sample 7 ..... 3-layer Polyolefin / No
tunneling in both 1
EVA core orientations
Avery Dennison Overlaminate / No tunneling in both 1
DOL 2060 PVC orientations
3M 8548 Overlaminate / No tunneling in both 1
Envision Gloss Polyurethane orientations
Avery Dennison Overlaminate/ Tunnels in both orientations 5
TOL 7060 Polyolefin
Avery Dennison Polyolefin Tunnels in both orientations 5
PE85 (polyethylene) film
[0046] As shown from the results in Table III, DOL 2060 and 3M 8548
Envision
Gloss (which is a polyurethane film) show similar performance in tunneling as
Sample 1.
However, the samples of PE 85 and TOL 7060 both show severe tunneling under
the testing
conditions.
[0047] Comparison testing between an overlaminate of the present
invention
and commercially-available products was also done to determine modulus and
tensile
properties. The modulus of each film was tested using Dynamic Mechanical
Analysis from TA
Instruments, and the samples were scanned from -50 C to 150 C at 1 Hz. The
modulus results
are shown in Table IV below and, as shown, the samples that showed no
tunneling have a lower
modulus at 70 C as compared to the samples that showed tunneling.
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[0048] In addition, the tensile properties of those films were
measured at room
temperature and at 70 C using Instron equipped with a temperature control
chamber. The
results are also shown in Table IV below. From these results, it may be
observed that the
samples that did not result in tunneling had a lower a lower modulus at 70 C
than the samples
that did result in tunneling. In addition, a digital mechanical analysis (DMA)
curve was prepared
as shown at Fig. 6, from which it may be observed (along with the data herein)
that if the
modulus is within an acceptable range at 70 C the film does not tunnel.
Table IV
!MIT T1111111111111111111 11111111110ii.40Ø00.6111111PMEME 1111(PgrilPsl
Avery PVC 47,825 71,381 283 883
Dennison
DOL 2060
Avery Polypropylene 44,855 78,168 12,264 15,998
Dennison Based film
TOL 7060
Avery Blend of 10,2781 98,291 31.422 20,647
Dennison PE HDPE/LLDPE
85
Sample 1 Polyolefin / 28,210 30,324 6,198 5,389
EVA blend
3M 8548 Polyurethane 51,203 31,804 9,757 8,146
Envision film
Gloss
Example III
[0049] In this example, film structures were created using the same
process as
described in to Example I but using a five-layer feedblock and five extruders.
The formulation
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for each extruder is provided in Table V below, and the layers of the film
were positioned in the
order provided in the table. The films of this example were created to
increase the modulus at
room temperature while maintaining a low temperature modulus at elevated
temperatures.
Table V
toteilAVetillin MCiitetaiietC Core L.ayer
Aties,etaitrie
amp e
minammummuosimpiminiAlommingimemoommommunigoosymemiiiiiiiimlioxymeng
93 % Surlyn 73 % 73 % 73 % 62 %
Petrothene
1803 Petrothene Petrothene Petrothene NA324-009
% Ampacet NA324-009 NA324-009 NA324-009 35 % Ethylene
8 UV 25 % Ethylene 25 % Ethylene 25 %
Ethylene vinyl acetate
2 % Ampacet vinyl acetate vinyl acetate vinyl
acetate 1 % Ampacet UV
Process Aid 1 % Ampacet 1 % Ampacet 1 % Ampacet 10561
UV 10561 UV 10561 UV 10561 0.5 %
Ampacet
0.5 % Ampacet 0.5 % Ampacet 0.5 % Ampacet Process aid
Process aid Process aid Process aid 0.5 % FRC-
2005
0.5 % FRC- 0.5 % FRC- 0.5 % FRC-
2005 2005 2005
93 % Surlyn 73 % Dow 73 % Dow 73 % Dow 62 % Dow
DMTA
1803 DMTA -8904 Petrothene DMTA -8904 -8904 NT 7
HDPE
5 % Ampacet NT 7 HDPE NA324-009 NT 7 HDPE 35 %
Ethylene
9 UV 25 % Ethylene 25 % Ethylene 25 %
Ethylene vinyl acetate
2 % Ampacet vinyl acetate vinyl acetate vinyl
acetate 1 % Ampacet UV
Process Aid 1 % Ampacet 1 % Ampacet 1 % Ampacet 10561
UV 10561 UV 10561 UV 10561 0.5 %
Ampacet
0.5 % Ampacet 0.5 % Ampacet 0.5 % Ampacet Process aid
Process aid Process aid Process aid 0.5 % FRC-
2005
0.5 % FRC- 0.5 % FRC- 0.5 % FRC-
2005 2005 2005
93 % Surlyn 73 % Dow 73 % Dow 73 % Dow 62 % Dow
DMTA
1803 DMTA -8904 DMTA -8904 DMTA -8904 -8904 NT 7
HDPE
5 % Ampacet NT 7 HDPE NT 7 HDPE NT 7 HDPE 35 %
Ethylene
UV 25 % Ethylene 25 % Ethylene 25 % Ethylene
vinyl acetate
2 % Ampacet vinyl acetate vinyl acetate vinyl
acetate 1 % Ampacet UV
Process Aid 1 % Ampacet 1 % Ampacet 1 % Ampacet 10561
UV 10561 UV 10561 UV 10561 0.5 %
Ampacet
0.5 % Ampacet 0.5 % Ampacet 0.5 % Ampacet Process aid
Process aid Process aid Process aid 0.5 % FRC-
2005
0.5 % FRC- 0.5 % FRC- 0.5 % FRC-
2005 2005 2005
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[0050] The films of Example III were coated with adhesive S8072,
available from
Avery Dennison Corporation, as described in Example I. The samples were then
tested for
tunneling using the test procedure described in Example I. The results are
reported in Table VI
below, and it was observed that the addition of ethylene vinyl acetate to the
core layer and the
adhesive layer minimizes tunneling during the thermal cycling of the laminate.
However, in
some embodiments, suitable results with minimal or no tunneling may be
obtained by the
inclusion of ethylene vinyl acetate only in the core layer.
Table VI
Sample iikiminin Woo 00).
Negligible in CD and
82 Pass
MD orientations
No tunneling in CD and
91 Pass
MD orientations
No tunneling in CD and
101 Pass
MD orientations
[0051] The films of Example III were also tested for flammability
based on
European Standard EN 13501-1. For this testing, a strip measuring one inch
strip by 6 inches
was laminated to an aluminum panel, and the laminated strip was exposed to a
burner for 30
seconds and then removed. A laminate was considered a pass if the entire
laminate did not
burn completely or if the flame did not grow larger than 6 inches. As
indicated in Table VI
above, all of the samples of Example III passed the burn test.
[0052] The optical and tensile properties of the overlaminate films
of Example III
also were compared with the current overlaminate product available from Avery
Dennison as
TOL 7060. The results are shown in Figures 7 and 8, wherein Sample 22613-01
correlates to
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Sample 8, Sample 22613-02 correlates to Sample 9, Sample 22613-03 correlates
to Sample 10,
Current TOL represents the commercially-available TOL 7060 product of Avery
Dennison
Corporation. From these results, it is apparent that the use of high density
is suitable for some
embodiments of the present invention and results in sufficient stiffness. In
addition, for certain
applications, medium density polyethylene, by itself, may not provide suitable
stiffness in the
film.
Example IV
[0053] In this example, film structures were extruded in the same manner as
described above for Example I, and the formulation for each layer is provided
in Table VII
below. The Tg of Topas 9903 D-10 is 35 C and the Tg of Topas 9506F-04 is 65
C.
Table VII
11111111111111111111111110. 11
100 % 100 % Huntsman LDPE 1017 100 % Huntsman LDPE 1017
11 Surlyn
1803
100 % 25 % Topas 9903 D-10 25 % Topas 9903 D-10
12 Surlyn 75 % Petrothene NA324-009 75 % Petrothene NA324-009
1803
100 % 25 % Topas 9903 D-10 25 % Topas 9903 D-10
13 Surlyn 25 % Ethylene vinyl acetate 25 % Ethylene vinyl acetate
1803 50 % Huntsman LDPE 1017 50 % Huntsman LDPE 1017
100 % 50 % Topas 9903 D-10 50 % Topas 9903 D-10
14 Surlyn 50 % Huntsman LDPE 1017 50 % Huntsman LDPE 1017
1803
100 % 25 % Topas 9506F-04 25 % Topas 9903 D-10
15 Surlyn 75 % Huntsman LDPE 1017 75 % Huntsman LDPE 1017
1803
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100 % 25 % Topas 9506F-04 25 % Topas 9903 D-10
16 Surlyn 25 % Ethylene vinyl acetate 25 % Ethylene vinyl acetate
1803 50 % Huntsman LDPE 1017 50 % Huntsman LDPE 1017
100 % 50 % Topas 9506F-04 50 % Topas 9903 D-10
17 Surlyn 50 % Huntsman LDPE 1017 50 % Huntsman LDPE 1017
1803
100 % 25 % Topas 9506F-04 25 % Topas 9506F-04
18 Surlyn 25 % Topas 9903D-10 25 % Topas 9903D-10
1803 50 % Huntsman LDPE 1017 50 % Huntsman LDPE 1017
100 % 15 % Topas 9506F-04 15 % Topas 9506F-04
19 Surlyn 15 % Topas 9903D-10 15 % Topas 9903D-10
1803 70 % Huntsman LDPE 1017 70 % Huntsman LDPE 1017
[0054] Each film was adhesive coated with S8072, an adhesive sold by Avery
Dennison Corporation, and the films were then laminated to a TrueImpact 7000
print layer,
which is sold by Avery Dennison Corporation. The samples were mounted onto a
coated
automotive panel substrate such that an overlap was created between two
segments of
overlaminated print film. The overlaminates were tested for tunneling as
described above and
mechanical properties were determined using Instron as described in previous
examples. The
results are provided in Table VIII below.
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Table VIII
lAoulus
Tunneling Tunretrg at rom Fm
Sample
commerits Rank temperature loss
psl............................................................................
..
Tunnels in both
11 5 N/A N/A
orientations
No tunneling in
12 1 59,530 98.3
both orientations
No tunneling in
13 1 31,681 99.2
both orientations
No tunneling in
14 1 65,593 50.9
both orientations
No tunneling in
15 1 57,361 77.3
both orientations
No tunneling in
16 1 58,037 86.0
both orientations
No tunneling in
17 1 149,833 95.6
both orientations
No tunneling in
18 1 117,733 89.6
both orientations
No tunneling in
19 1 70,284 91.8
both orientations
[0055] From the results in Table VIII, it was observed that
including amorphous
olefin copolymers having a Tg above 25 C and below 70 C improved the room
temperature
tensile properties of the film, which are essential for handling during
application and also
reduce or eliminate tunneling when the film is exposed to elevated temperature
conditions like
70 C. Without intending to be bound by theory, it is believed that the
reduction of tunneling is
due to significant modulus decrease resulted from softening of the amorphous
olefin
copolymer 70 C.
[0056] The modulus values measured at room temperature and at 70 C
of
certain formulations from Example III and Example IV reported below in Table
IX.
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Table IX
12 60,870 5246 None
13 52,359 2194 None
14 51,947 1429 None
18 130,704 1,456 None
19 73,881 3,336 None
9 38,593 5,753 None
[0057] As shown in the results in Table IX, the films tested did
not show any
tunneling. Notably, the modulus at 70 C for each of these films was
significantly lower than the
corresponding modulus for films that demonstrated tunneling in other examples.
[0058] In some embodiments, overlaminates of the present invention
may also
include or have applied thereto a top coating. Such top coatings may be one
layer and applied
to the overlaminate, such as adjacent to the skin layer. Top coatings may be
comprised of any
suitable materials. In certain embodiments, top coatings may comprise polymers
containing
acrylic, ester, urethane, or blends thereof. The top coating may enhance the
adhesion at the
seaming area of overlapping segments (as illustrated in Fig. 5 and Fig. 9),
i.e., the adhesion
between the adhesion on the surface of the overlaminate. In addition, any
additional decals or
materials may be readily adhered to the top coating, which, in some
embodiments, may have
better adhesion to such items as compared with the skin layer. For example,
some
advertisements may include an overlaminate and an advertiser may wish to
adhere additional
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information to the advertisement, such as sign-cut phone number or logo. In
such instances,
materials conveying the additional information, called an overpost or
overposting, may be
adhered to the top coating. The following Example V provides additional
disclosure of
illustrative embodiments of this nature.
Example VI
[0059] Two different rolls of films made in were used in this
example. For a first
roll, the skin layer (surlyn) was prepared according to the formulation of
Sample 9 and was then
corona treated to 50-52 dynes. Then, the film was coated with a top coating,
which is used
particularly in the product Fasson 2 Mil Clear BOPP TC available from Avery
Dennison
Corporation (Spec# 78148). For the second roll, the film was prepared using
the formulation of
Sample 8. Then, the film was passed through a flame treatment at 100 ft/min to
treat the skin
(surlyn) layer, and the surface energy of the treated film was measured to be
58 dynes. Both
the coated and flame-treated films were then coated with pressure sensitive
adhesive to the
adhesive layer and laminated with liner. The adhesive and liner used were the
same as those
used in Avery Dennison's commercially available D0L2060 gloss products.
Samples were taken
from both rolls and laminated with True Impact (TMP) 7000 materials, available
from Avery
Dennison Corporation.
[0060] Each sample was then placed on the roof and side panels of a
car to
create an overlap as illustrated in Figure 5. The samples on the roof were
evaluated for
tunneling and the samples on the side panels were washed with high pressure
hoses for at least
one minute and evaluated for delamination at the seaming area. Two control
samples, namely
DOL 2060 gloss and TOL 7060, both sold by Avery Dennison Corporation, were
also used, and
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these samples were neither coated nor flame treated. The car was used under
normal driving
conditions and was always parked outdoors. The highest outdoor temperature
during the test
was 100 F, but the actual highest temperature of the on the car roof may have
exceed 160 F.
The results are shown in Table X below.
Table XI
Overlap
Tunneling delamination at
Sample Description Location on Car Ranking after seaming area
4 weeks after pressure
wash
TC-Coated Overlaminate Roof 1 NM
TC-Coated overlaminate Side panel NM No
Flame-treated overlaminate Roof 1 NM
Flame-treated overlaminate Side panel NM No
Overlaminate
Roof 1 NM
(no coating/flame treatment)
Overlaminate
Side panel NM Yes
(no coating/flame treatment)
TOL 7060 Roof 5 NM
TOL 7060 Side panel NM Yes
DOL 2060 Roof 1 NM
DOL 2060 Side panel NM No
*NM indicates not measured
[0061] It was observed that the adhesion of an the seaming area of
overlap film
to the surface of the overlaminate film was improved by either coating the
film with TC coating
or flame treatment, and such coatings did not affect the resistance of the
film to tunneling.
Other coatings that may be suitable include, without limitation, coatings such
as Neorez
waterborne coatings sold by DSM and acrylic coatings sold under the tradename
NeoCryl by
DSM.
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[0062] Embodiments of the present invention may used for any
suitable
purpose. In some embodiments, films of the present invention may be used as
overlaminates
for signs, posters, banners, vehicle signage applications, and other printed
materials. As
described above, embodiments of overlaminates of the present invention may be
used on
materials for indoor and/or outdoor display. In addition, as demonstrated by
the examples
above, films of the present invention may desirably avoid tunneling effects in
some
embodiments.
[0063] In addition, films of the present invention may be prepared
using any
suitable process. By way of example, films of the present invention may be
prepared using cast
film processes, blown film processes, and extrusion and coextrusion processes.
[0064] These and other modifications and variations to the present
invention
may be practiced by those of ordinary skill in the art without departing from
the spirit and
scope of the present invention, which is more particularly set forth in the
appended claims. In
addition, it should be understood that aspects of the various embodiments may
be
interchanged in whole or in part. Furthermore, those of ordinary skill in the
art will appreciate
that the foregoing description is by way of example only, and it is not
intended to limit the
invention as further described in such appended claims. Therefore, the spirit
and scope of the
appended claims should not be limited to the exemplary description of the
versions contained
he
28
